Natural Oil Metathesis Compositions and Methods

ABSTRACT

A metathesized natural oil composition comprising (i) a mixture olefins and/or esters, or (ii) a metathesized natural oil, is disclosed. The metathesized natural oil composition has a number average molecular weight in the range from about 100 g/mol to about 150,000 g/mol, a weight average molecular weight in the range from about 1,000 g/mol to about 100,000 g/mol, a z-average molecular weight in the range from about 5,000 g/mol to about 1,000,000 g/mol, and a polydispersity index of about 1 to about 20. The metathesized natural oil composition is metathesized at least once.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 13/922,626, filed Jun. 20, 2013, which claims the benefit ofpriority of U.S. Provisional Application No. 61/662,318, filed Jun. 20,2012 and U.S. Provisional Application No. 61/781,892, filed Mar. 14,2013; the disclosures of all of which are incorporated herein byreference in their entireties.

BACKGROUND

In recent years, there has been an increased demand for environmentallyfriendly techniques for manufacturing materials typically derived frompetroleum sources. In view of the non-renewable nature of petroleum, itis highly desirable to provide non-petroleum alternatives for materialmanufacturing biofuels, waxes, plastics, cosmetics, personal care items,and the like. One of the methods to manufacture such materials isthrough generating compositions through the metathesis of natural oilfeedstocks, such as vegetable and seed-based oils.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a schematic diagram of a process to produce ametathesized natural oil product and a transesterified product from anatural oil.

FIG. 2 depicts a mass spectrum of a metathesized natural oil product.

FIG. 3 depicts a mass spectrum of a metathesized natural oil product.

FIG. 4 depicts a mass spectrum of a metathesized natural oil product.

FIG. 5 depicts a mass spectrum of a metathesized natural oil product.

DETAILED DESCRIPTION

It is to be understood that unless specifically stated otherwise,references to “a,” “an,” and/or “the” may include one or more than one,and that reference to an item in the singular may also include the itemin the plural.

The terms “natural oils,” “natural feedstocks,” or “natural oilfeedstocks” may refer to oils derived from plants or animal sources. Theterm “natural oil” includes natural oil derivatives, unless otherwiseindicated. The terms also include modified plant or animal sources(e.g., genetically modified plant or animal sources), unless indicatedotherwise. Examples of natural oils include, but are not limited to,vegetable oils, algae oils, fish oils, animal fats, tall oils,derivatives of these oils, combinations of any of these oils, and thelike. Representative non-limiting examples of vegetable oils includecanola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, oliveoil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil,sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil,mustard oil, pennycress oil, camelina oil, and castor oil.Representative non-limiting examples of animal fats include lard,tallow, poultry fat, yellow grease, and fish oil. Tall oils areby-products of wood pulp manufacture.

The term “natural oil derivatives” refers to derivatives thereof derivedfrom natural oil. The methods used to form these natural oil derivativesmay include one or more of addition, neutralization, overbasing,saponification, transesterification, esterification, amidification,hydrogenation, isomerization, oxidation, alkylation, acylation,sulfurization, sulfonation, rearrangement, reduction, fermentation,pyrolysis, hydrolysis, liquefaction, anaerobic digestion, hydrothermalprocessing, gasification or a combination of two or more thereof.Examples of natural derivatives thereof may include carboxylic acids,gums, phospholipids, soapstock, acidulated soapstock, distillate ordistillate sludge, fatty acids, fatty acid esters, as well as hydroxysubstituted variations thereof, including unsaturated polyol esters. Insome embodiments, the natural oil derivative may comprise an unsaturatedcarboxylic acid having from about 5 to about 30 carbon atoms, having oneor more carbon-carbon double bonds in the hydrocarbon (alkene) chain.The natural oil derivative may also comprise an unsaturated fatty acidalkyl (e.g., methyl) ester derived from a glyceride of natural oil. Forexample, the natural oil derivative may be a fatty acid methyl ester(“FAME”) derived from the glyceride of the natural oil. In someembodiments, a feedstock includes canola or soybean oil, as anon-limiting example, refined, bleached, and deodorized soybean oil(i.e., RBD soybean oil).

The term “low-molecular-weight olefin” may refer to any one orcombination of unsaturated straight, branched, or cyclic hydrocarbons inthe C₂ to C₁₄ range. Low-molecular-weight olefins include“alpha-olefins” or “terminal olefins,” wherein the unsaturatedcarbon-carbon bond is present at one end of the compound.Low-molecular-weight olefins may also include dienes or trienes.Examples of low-molecular-weight olefins in the C₂ to C₆ range include,but are not limited to: ethylene, propylene, 1-butene, 2-butene,isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene,2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1-hexene, 2-hexene,3-hexene, 4-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene,4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. Other possiblelow-molecular-weight olefins include styrene and vinyl cyclohexane. Incertain embodiments, it is preferable to use a mixture of olefins, themixture comprising linear and branched low-molecular-weight olefins inthe C₄-C₁₀ range. In one embodiment, it may be preferable to use amixture of linear and branched C₄ olefins (i.e., combinations of:1-butene, 2-butene, and/or isobutene). In other embodiments, a higherrange of C₁₁-C₀₁4 may be used.

The term “metathesis monomer” refers to a single entity that is theproduct of a metathesis reaction which comprises a molecule of acompound with one or more carbon-carbon double bonds which has undergonean alkylidene unit interchange via one or more of the carbon-carbondouble bonds either within the same molecule (intramolecular metathesis)and/or with a molecule of another compound containing one or morecarbon-carbon double bonds such as an olefin (intermolecularmetathesis).

The term “metathesis dimer” refers to the product of a metathesisreaction wherein two reactant compounds, which can be the same ordifferent and each with one or more carbon-carbon double bonds, arebonded together via one or more of the carbon-carbon double bonds ineach of the reactant compounds as a result of the metathesis reaction.

The term “metathesis trimer” refers to the product of one or moremetathesis reactions wherein three molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the trimer containing threebonded groups derived from the reactant compounds.

The term “metathesis tetramer” refers to the product of one or moremetathesis reactions wherein four molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the tetramer containing fourbonded groups derived from the reactant compounds.

The term “metathesis pentamer” refers to the product of one or moremetathesis reactions wherein five molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the pentamer containing fivebonded groups derived from the reactant compounds.

The term “metathesis hexamer” refers to the product of one or moremetathesis reactions wherein six molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the hexamer containing sixbonded groups derived from the reactant compounds.

The term “metathesis heptamer” refers to the product of one or moremetathesis reactions wherein seven molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the heptamer containing sevenbonded groups derived from the reactant compounds.

The term “metathesis octamer” refers to the product of one or moremetathesis reactions wherein eight molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the octamer containing eightbonded groups derived from the reactant compounds.

The term “metathesis nonamer” refers to the product of one or moremetathesis reactions wherein nine molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the nonamer containing ninebonded groups derived from the reactant compounds.

The term “metathesis decamer” refers to the product of one or moremetathesis reactions wherein ten molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the decamer containing tenbonded groups derived from the reactant compounds.

The term “metathesis oligomer” refers to the product of one or moremetathesis reactions wherein two or more molecules (e.g., 2 to about 10,or 2 to about 4) of two or more reactant compounds, which can be thesame or different and each with one or more carbon-carbon double bonds,are bonded together via one or more of the carbon-carbon double bonds ineach of the reactant compounds as a result of the one or more metathesisreactions, the oligomer containing a few (e.g., 2 to about 10, or 2 toabout 4) bonded groups derived from the reactant compounds. In someembodiments, the term “metathesis oligomer” may include metathesisreactions wherein greater than ten molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the oligomer containing greaterthan ten bonded groups derived from the reactant compounds.

As used herein, the terms “metathesize” and “metathesizing” may refer tothe reacting of a natural oil feedstock in the presence of a metathesiscatalyst to form a metathesized natural oil product comprising a newolefinic compound and/or esters. Metathesizing may refer tocross-metathesis (a.k.a. co-metathesis), self-metathesis, ring-openingmetathesis, ring-opening metathesis polymerizations (“ROMP”),ring-closing metathesis (“RCM”), and acyclic diene metathesis (“ADMET”).As a non-limiting example, metathesizing may refer to reacting twotriglycerides present in a natural feedstock (self-metathesis) in thepresence of a metathesis catalyst, wherein each triglyceride has anunsaturated carbon-carbon double bond, thereby forming an oligomerhaving a new mixture of olefins and esters that may comprise one or moreof: metathesis monomers, metathesis dimers, metathesis trimers,metathesis tetramers, metathesis pentamers, and higher order metathesisoligomers (e.g., metathesis hexamers, metathesis, metathesis heptamers,metathesis octamers, metathesis nonamers, metathesis decamers, andhigher than metathesis decamers and above).

Metathesis is a catalytic reaction generally known in the art thatinvolves the interchange of alkylidene units among compounds containingone or more double bonds (e.g., olefinic compounds) via the formationand cleavage of the carbon-carbon double bonds. Metathesis may occurbetween two like molecules (often referred to as self-metathesis) and/orit may occur between two different molecules (often referred to ascross-metathesis). Self-metathesis may be represented schematically asshown in Equation A below.

R¹—CH═CH—R²+R¹—CH═CH—R²↔R¹—CH═CH—R¹+R²—CH═CH—R²  Equation A

wherein R¹ and R² are organic groups.

Cross-metathesis may be represented schematically as shown in Equation Bbelow.

R¹—CH═CH—R²+R³—CH═CH—R⁴↔R¹—CH═CH—R³+R¹—CH═CH—R⁴+R²—CH═CH—R³+R²—CH═CH—R⁴+R¹—CH═CH—R¹+R²—CH═CH—R²+R³—CH═CH—R³+R⁴—CH═CH—R⁴  EquationB

wherein R¹, R², R³, and R⁴ are organic groups.

The metathesis reaction of the natural oil feedstock having polyolesters (of fatty acids) results in the oligomerization of the naturaloil feedstock having a mixture of olefins and esters that may compriseone or more of: metathesis monomers, metathesis dimers, metathesistrimers, metathesis tetramers, metathesis pentamers, and higher ordermetathesis oligomers (e.g., metathesis hexamers, metathesis heptamers,metathesis octamers, metathesis nonamers, metathesis decamers, andhigher than metathesis decamers).

Natural oils of the type described herein typically are composed oftriglycerides of fatty acids. These fatty acids may be either saturated,monounsaturated or polyunsaturated and contain varying chain lengthsranging from C₈ to C₃₀. The most common fatty acids include saturatedfatty acids such as lauric acid (dodecanoic acid), myristic acid(tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid(octadecanoic acid), arachidic acid (eicosanoic acid), and lignocericacid (tetracosanoic acid); unsaturated acids include such fatty acids aspalmitoleic (a C16 acid), and oleic acid (a C18 acid); polyunsaturatedacids include such fatty acids as linoleic acid (a di-unsaturated C18acid), linolenic acid (a tri-unsaturated C18 acid), and arachidonic acid(a tetra-unsubstituted C20 acid). The natural oils are further comprisedof esters of these fatty acids in random placement onto the three sitesof the trifunctional glycerine molecule. Different natural oils willhave different ratios of these fatty acids, and within a given naturaloil there is a range of these acids as well depending on such factors aswhere a vegetable or crop is grown, maturity of the vegetable or crop,the weather during the growing season, etc. Thus, it is difficult tohave a specific or unique structure for any given natural oil, butrather a structure is typically based on some statistical average. Forexample soybean oil contains a mixture of stearic acid, oleic acid,linoleic acid, and linolenic acid in the ratio of 15:24:50:11, and anaverage number of double bonds of 4.4-4.7 per triglyceride. One methodof quantifying the number of double bonds is the iodine value (IV) whichis defined as the number of grams of iodine that will react with 100grams of vegetable oil. Therefore for soybean oil, the average iodinevalue range is from 120-140. Soybean oil may comprises about 95% byweight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. Major fatty acids in the polyol esters of soybean oil includesaturated fatty acids, as a non-limiting example, palmitic acid(hexadecanoic acid) and stearic acid (octadecanoic acid), andunsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9, 12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

When a polyol ester comprises molecules having more than onecarbon-carbon double bond, self-metathesis may result in oligomerizationor polymerization of the unsaturates in the starting material. Forexample, Equation C depicts metathesis oligomerization of arepresentative species (e.g., a polyol ester) having more than onecarbon-carbon double bond. In Equation C, the self-metathesis reactionresults in the formation of metathesis dimers, metathesis trimers, andmetathesis tetramers. Although not shown, higher order oligomers such asmetathesis pentamers, hexamers, heptamers, octamers, nonamers, decamers,and higher than decamers, and mixtures of two or more thereof, may alsobe formed. The number of metathesis repeating units or groups in themetathesized natural oil may range from 1 to about 100, or from 2 toabout 50, or from 2 to about 30, or from 2 to about 10, or from 2 toabout 4. The molecular weight of the metathesis dimer may be greaterthan the molecular weight of the unsaturated polyol ester from which thedimer is formed. Each of the bonded polyol ester molecules may bereferred to as a “repeating unit or group.” Typically, a metathesistrimer may be formed by the cross-metathesis of a metathesis dimer withan unsaturated polyol ester. Typically, a metathesis tetramer may beformed by the cross-metathesis of a metathesis trimer with anunsaturated polyol ester or formed by the cross-metathesis of twometathesis dimers.

R¹—HC═CH—R²—HC═CH—R³+R¹—HC═CH—R²—HC═CH—R³↔R¹—HC═CH—R²—HC═CH—R²—HC═CH—R³+(otherproducts)  Equation C

Metathesis Dimer

R¹—R²—HC═CH—R²—HC═CH—R³+R¹—HC═CH—R²—HC═CH—R³↔R¹—HC═CH—R²—HC═CH—R²—HC═CH—R²—HC═CH—R³+(otherproducts)

Metathesis Trimer

R¹—HC═CH—R²—HC═CH—R²—HC═CH—R²—HC═CH—R³+R¹—HC═CH—R²—HC═CH—R³↔R¹—HC═CH—R²—HC═CH—R²—HC═CH—R²—HC═CH—R²—HC═CH—R³+(otherproducts)

Metathesis Tetramer

where R¹, R², and R³ are organic groups.

As noted, the self-metathesis of the natural oil occurs in the presenceof a metathesis catalyst. As stated previously, the term “metathesiscatalyst” includes any catalyst or catalyst system that catalyzes ametathesis reaction. Any known metathesis catalyst may be used, alone orin combination with one or more additional catalysts. Suitablehomogeneous metathesis catalysts include combinations of a transitionmetal halide or oxo-halide (e.g., WOCl₄ or WCl₆) with an alkylatingcocatalyst (e.g., Me₄Sn), or alkylidene (or carbene) complexes oftransition metals, particularly Ru, Mo, or W. These include first andsecond-generation Grubbs catalysts, Grubbs-Hoveyda catalysts, and thelike. Suitable alkylidene catalysts have the general structure:

M[X¹X²L¹L²(L³)_(n)]=C_(m)═C(R¹)R²

where M is a Group 8 transition metal, L¹, L², and L³ are neutralelectron donor ligands, n is 0 (such that L³ may not be present) or 1, mis 0, 1, or 2, X¹ and X² are anionic ligands, and R¹ and R² areindependently selected from H, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, and functional groups. Any two or more of X¹, X², L¹, L²,L³, R¹ and R² can form a cyclic group and any one of those groups can beattached to a support.

First-generation Grubbs catalysts fall into this category where m=n=0and particular selections are made for n, X¹, X², L¹, L², L³, R¹ and R²as described in U.S. Pat. Appl. Publ. No. 2010/0145086, the teachings ofwhich related to all metathesis catalysts are incorporated herein byreference.

Second-generation Grubbs catalysts also have the general formuladescribed above, but L¹ is a carbene ligand where the carbene carbon isflanked by N, O, S, or P atoms, preferably by two N atoms. Usually, thecarbene ligand is part of a cyclic group. Examples of suitablesecond-generation Grubbs catalysts also appear in the '086 publication.

In another class of suitable alkylidene catalysts, L¹ is a stronglycoordinating neutral electron donor as in first- and second-generationGrubbs catalysts, and L² and L³ are weakly coordinating neutral electrondonor ligands in the form of optionally substituted heterocyclic groups.Thus, L² and L³ are pyridine, pyrimidine, pyrrole, quinoline, thiophene,or the like.

In yet another class of suitable alkylidene catalysts, a pair ofsubstituents is used to form a bi- or tridentate ligand, such as abiphosphine, dialkoxide, or alkyldiketonate. Grubbs-Hoveyda catalystsare a subset of this type of catalyst in which L² and R² are linked.Typically, a neutral oxygen or nitrogen coordinates to the metal whilealso being bonded to a carbon that is α-, β-, or γ- with respect to thecarbene carbon to provide the bidentate ligand. Examples of suitableGrubbs-Hoveyda catalysts appear in the '086 publication.

The structures below provide just a few illustrations of suitablecatalysts that may be used:

Heterogeneous catalysts suitable for use in the self- orcross-metathesis reaction include certain rhenium and molybdenumcompounds as described, e.g., by J. C. Mol in Green Chem. 4 (2002) 5 atpp. 11-12. Particular examples are catalyst systems that include Re₂O₇on alumina promoted by an alkylating cocatalyst such as a tetraalkyl tinlead, germanium, or silicon compound. Others include MoCl₃ or MoCl₅ onsilica activated by tetraalkyltins.

For additional examples of suitable catalysts for self- orcross-metathesis, see U.S. Pat. Nos. 4,545,941, 5,312,940, 5,342,909,5,710,298, 5,728,785, 5,728,917, 5,750,815, 5,831,108, 5,922,863,6,306,988, 6,414,097, 6,696,597, 6,794,534, 7,102,047, 7,378,528, andU.S. Pat. Appl. Publ. No. 2009/0264672 A1, and PCT/US2008/009635, pp.18-47, all of which are incorporated herein by reference. A number ofmetathesis catalysts that may be advantageously employed in metathesisreactions are manufactured and sold by Materia, Inc. (Pasadena, Calif.).

A process for metathesizing a natural oil and treating the resultingmetathesized natural oil is illustrated in FIG. 1. In certainembodiments, prior to the metathesis reaction, a natural oil feedstockmay be treated to render the natural oil more suitable for thesubsequent metathesis reaction. In one embodiment, the treatment of thenatural oil involves the removal of catalyst poisons, such as peroxides,which may potentially diminish the activity of the metathesis catalyst.Non-limiting examples of natural oil feedstock treatment methods todiminish catalyst poisons include those described in PCT/US2008/09604,PCT/US2008/09635, and U.S. patent application Ser. Nos. 12/672,651 and12/672,652, herein incorporated by reference in their entireties. Incertain embodiments, the natural oil feedstock is thermally treated byheating the feedstock to a temperature greater than 100° C. in theabsence of oxygen and held at the temperature for a time sufficient todiminish catalyst poisons in the feedstock. In other embodiments, thetemperature is between approximately 100° C. and 300° C., betweenapproximately 120° C. and 250° C., between approximately 150° C. and210° C., or approximately between 190 and 200° C. In one embodiment, theabsence of oxygen is achieved by sparging the natural oil feedstock withnitrogen, wherein the nitrogen gas is pumped into the feedstocktreatment vessel at a pressure of approximately 10 atm (150 psig).

In certain embodiments, the natural oil feedstock is chemically treatedunder conditions sufficient to diminish the catalyst poisons in thefeedstock through a chemical reaction of the catalyst poisons. Incertain embodiments, the feedstock is treated with a reducing agent or acation-inorganic base composition. Non-limiting examples of reducingagents include bisulfate, borohydride, phosphine, thiosulfate, andcombinations thereof.

In certain embodiments, the natural oil feedstock is treated with anadsorbent to remove catalyst poisons. In one embodiment, the feedstockis treated with a combination of thermal and adsorbent methods. Inanother embodiment, the feedstock is treated with a combination ofchemical and adsorbent methods. In another embodiment, the treatmentinvolves a partial hydrogenation treatment to modify the natural oilfeedstock's reactivity with the metathesis catalyst. Additionalnon-limiting examples of feedstock treatment are also described belowwhen discussing the various metathesis catalysts.

Additionally, in certain embodiments, the low-molecular-weight olefinmay also be treated prior to the metathesis reaction. Like the naturaloil treatment, the low-molecular-weight olefin may be treated to removepoisons that may impact or diminish catalyst activity.

As shown in FIG. 1, after this optional treatment of the natural oilfeedstock and/or low-molecular-weight olefin, the natural oil 12 isreacted with itself, or combined with a low-molecular-weight olefin 14in a metathesis reactor 20 in the presence of a metathesis catalyst. Insome embodiments, the natural oil 12 is soybean oil. Metathesiscatalysts and metathesis reaction conditions are discussed in greaterdetail below. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil 12 undergoes a self-metathesis reaction withitself. In other embodiments, in the presence of the metathesiscatalyst, the natural oil 12 undergoes a cross-metathesis reaction withthe low-molecular-weight olefin 14. In certain embodiments, the naturaloil 12 undergoes both self- and cross-metathesis reactions in parallelmetathesis reactors. Multiple, parallel, or sequential metathesisreactions (at least one or more times) may be conducted. Theself-metathesis and/or cross-metathesis reaction form a metathesizednatural oil product 22 wherein the metathesized natural oil product 22comprises olefins 32 and esters 34. In some embodiments, metathesizednatural oil product 22 is metathesized soybean oil (MSBO). As usedherein, “metathesized natural oil product” may also be referred to inthe equivalent as “metathesized natural oil composition.”

In certain embodiments, the low-molecular-weight olefin 14 is in the C₂to C₆ range. As a non-limiting example, in one embodiment, thelow-molecular-weight olefin 14 may comprise at least one of thefollowing: ethylene, propylene, 1-butene, 2-butene, isobutene,1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene, 2-methyl-2-butene,3-methyl-1-butene, cyclopentene, 1-hexene, 2-hexene, 3-hexene, 4-hexene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, and cyclohexene. In another embodiment, thelow-molecular-weight olefin 14 comprises at least one of styrene andvinyl cyclohexane. In another embodiment, the low-molecular-weightolefin 14 may comprise at least one of ethylene, propylene, 1-butene,2-butene, and isobutene. In another embodiment, the low-molecular-weightolefin 14 comprises at least one alpha-olefin or terminal olefin in theC₂ to C₁₀ range.

In another embodiment, the low-molecular-weight olefin 14 comprises atleast one branched low-molecular-weight olefin in the C₄ to C₁₀ range.Non-limiting examples of branched low-molecular-weight olefins includeisobutene, 3-methyl-1-butene, 2-methyl-3-pentene, and2,2-dimethyl-3-pentene. By using these branched low-molecular-weightolefins in the metathesis reaction, the methathesized natural oilproduct will include branched olefins, which can be subsequentlyhydrogenated to iso-paraffins. In certain embodiments, the branchedlow-molecular-weight olefins may help achieve the desired performanceproperties for a fuel composition, such as jet, kerosene, or dieselfuel.

As noted, it is possible to use a mixture of various linear or branchedlow-molecular-weight olefins in the reaction to achieve the desiredmetathesis product distribution. In one embodiment, a mixture of butenes(1-butene, 2-butenes, and, optionally, isobutene) may be employed as thelow-molecular-weight olefin, offering a low cost, commercially availablefeedstock instead a purified source of one particular butene. Such lowcost mixed butene feedstocks are typically diluted with n-butane and/orisobutane.

In certain embodiments, recycled streams from downstream separationunits may be introduced to the metathesis reactor 20 in addition to thenatural oil 12 and, in some embodiments, the low-molecular-weight olefin14. For instance, in some embodiments, a C₂-C₆ recycle olefin stream ora C₃-C₄ bottoms stream from an overhead separation unit may be returnedto the metathesis reactor. In one embodiment, as shown in FIG. 1, alight weight olefin stream 44 from an olefin separation unit 40 may bereturned to the metathesis reactor 20. In another embodiment, the C₃-C₄bottoms stream and the light weight olefin stream 44 are combinedtogether and returned to the metathesis reactor 20. In anotherembodiment, a C₁₅₊ bottoms stream 46 from the olefin separation unit 40is returned to the metathesis reactor 20. In another embodiment, all ofthe aforementioned recycle streams are returned to the metathesisreactor 20.

The metathesis reaction in the metathesis reactor 20 produces ametathesized natural oil product 22. In one embodiment, the metathesizednatural oil product 22 enters a flash vessel operated under temperatureand pressure conditions which target C₂ or C₂-C₃ compounds to flash offand be removed overhead. The C₂ or C₂-C₃ light ends are comprised of amajority of hydrocarbon compounds having a carbon number of 2 or 3. Incertain embodiments, the C₂ or C₂-C₃ light ends are then sent to anoverhead separation unit, wherein the C₂ or C₂-C₃ compounds are furtherseparated overhead from the heavier compounds that flashed off with theC₂-C₃ compounds. These heavier compounds are typically C₃-C₅ compoundscarried overhead with the C₂ or C₂-C₃ compounds. After separation in theoverhead separation unit, the overhead C₂ or C₂-C₃ stream may then beused as a fuel source. These hydrocarbons have their own value outsidethe scope of a fuel composition, and may be used or separated at thisstage for other valued compositions and applications. In certainembodiments, the bottoms stream from the overhead separation unitcontaining mostly C₃-C₅ compounds is returned as a recycle stream to themetathesis reactor. In the flash vessel, the metathesized natural oilproduct 22 that does not flash overhead is sent downstream forseparation in a separation unit 30, such as a distillation column.

Prior to the separation unit 30, in certain embodiments, themetathesized natural oil product 22 may be introduced to an adsorbentbed to facilitate the separation of the metathesized natural oil product22 from the metathesis catalyst. In one embodiment, the adsorbent is aclay bed. The clay bed will adsorb the metathesis catalyst, and after afiltration step, the metathesized natural oil product 22 can be sent tothe separation unit 30 for further processing. Separation unit 30 maycomprise a distillation unit. In some embodiments, the distillation maybe conducted, for example, by steam stripping the metathesized naturaloil product. Distilling may be accomplished by sparging the mixture in avessel, typically agitated, by contacting the mixture with a gaseousstream in a column that may contain typical distillation packing (e.g.,random or structured), by vacuum distillation, or evaporating the lightsin an evaporator such as a wiped film evaporator. Typically, steamstripping will be conducted at reduced pressure and at temperaturesranging from about 100° C. to 250° C. The temperature may depend, forexample, on the level of vacuum used, with higher vacuum allowing for alower temperature and allowing for a more efficient and completeseparation of volatiles.

In another embodiment, the adsorbent is a water soluble phosphinereagent such as tris hydroxymethyl phosphine (THMP). Catalyst may beseparated with a water soluble phosphine through known liquid-liquidextraction mechanisms by decanting the aqueous phase from the organicphase. In other embodiments, the metathesized natural oil product 22 maybe contacted with a reactant to deactivate or to extract the catalyst.

In the separation unit 30, in certain embodiments, the metathesizednatural oil product 22 is separated into at least two product streams.In one embodiment, the metathesized natural oil product 22 is sent tothe separation unit 30, or distillation column, to separate the olefins32 from the esters 34. In another embodiment, a byproduct streamcomprising C₇'s and cyclohexadiene may be removed in a side-stream fromthe separation unit 30. In certain embodiments, the separated olefins 32may comprise hydrocarbons with carbon numbers up to 24. In certainembodiments, the esters 34 may comprise metathesized glycerides. Inother words, the lighter end olefins 32 are preferably separated ordistilled overhead for processing into olefin compositions, while theesters 34, comprised mostly of compounds having carboxylic acid/esterfunctionality, are drawn into a bottoms stream. Based on the quality ofthe separation, it is possible for some ester compounds to be carriedinto the overhead olefin stream 32, and it is also possible for someheavier olefin hydrocarbons to be carried into the ester stream 34.

In one embodiment, the olefins 32 may be collected and sold for anynumber of known uses. In other embodiments, the olefins 32 are furtherprocessed in an olefin separation unit 40 and/or hydrogenation unit 50(where the olefinic bonds are saturated with hydrogen gas 48, asdescribed below). In other embodiments, esters 34 comprising heavier endglycerides and free fatty acids are separated or distilled as a bottomsproduct for further processing into various products. In certainembodiments, further processing may target the production of thefollowing non-limiting examples: fatty acid methyl esters; biodiesel;9DA esters, 9UDA esters, and/or 9DDA esters; 9DA, 9UDA, and/or 9DDA;alkali metal salts and alkaline earth metal salts of 9DA, 9UDA, and/or9DDA; diacids, and/or diesters of the transesterified products; andmixtures thereof. In certain embodiments, further processing may targetthe production of C₁₅-C₁₈ fatty acids and/or esters. In otherembodiments, further processing may target the production of diacidsand/or diesters. In yet other embodiments, further processing may targetthe production of compounds having molecular weights greater than themolecular weights of stearic acid and/or linolenic acid.

As shown in FIG. 1, regarding the overhead olefins 32 from theseparation unit 30, the olefins 32 may be further separated or distilledin the olefin separation unit 40 to separate the stream's variouscomponents. In one embodiment, light end olefins 44 consisting of mainlyC₂-C₉ compounds may be distilled into an overhead stream from the olefinseparation unit 40. In certain embodiments, the light end olefins 44 arecomprised of a majority of C₃-C₈ hydrocarbon compounds. In otherembodiments, heavier olefins having higher carbon numbers may beseparated overhead into the light end olefin stream 44 to assist intargeting a specific fuel composition. The light end olefins 44 may berecycled to the metathesis reactor 20, purged from the system forfurther processing and sold, or a combination of the two. In oneembodiment, the light end olefins 44 may be partially purged from thesystem and partially recycled to the metathesis reactor 20. With regardsto the other streams in the olefin separation unit 40, a heavier C₁₆₊,C₁₈₊, C₂₀₊, C₂₂₊, or C₂₄₊ compound stream may be separated out as anolefin bottoms stream 46. This olefin bottoms stream 46 may be purged orrecycled to the metathesis reactor 20 for further processing, or acombination of the two. In another embodiment, a center-cut olefinstream 42 may be separated out of the olefin distillation unit forfurther processing. The center-cut olefins 42 may be designed to targeta selected carbon number range for a specific fuel composition. As anon-limiting example, a C₅-C₁₅ distribution may be targeted for furtherprocessing into a naphtha-type jet fuel. Alternatively, a C₈-C₁₆distribution may be targeted for further processing into a kerosene-typejet fuel. In another embodiment, a C₈-C₂₅ distribution may be targetedfor further processing into a diesel fuel.

In certain embodiments, the olefins 32 may be oligomerized to formpoly-alpha-olefins (PAOs) or poly-internal-olefins (PIOs), mineral oilsubstitutes, and/or biodiesel fuel. The oligomerization reaction maytake place after the distillation unit 30 or after the overhead olefinseparation unit 40. In certain embodiments, byproducts from theoligomerization reactions may be recycled back to the metathesis reactor20 for further processing.

As mentioned, in one embodiment, the olefins 32 from the separation unit30 may be sent directly to the hydrogenation unit 50. In anotherembodiment, the center-cut olefins 42 from the overhead olefinseparation unit 40 may be sent to the hydrogenation unit 50.Hydrogenation may be conducted according to any known method in the artfor hydrogenating double bond-containing compounds such as the olefins32 or center-cut olefins 42. In certain embodiments, in thehydrogenation unit 50, hydrogen gas 48 is reacted with the olefins 32 orcenter-cut olefins 42 in the presence of a hydrogenation catalyst toproduce a hydrogenated product 52.

In some embodiments, the olefins are hydrogenated in the presence of ahydrogenation catalyst comprising nickel, copper, palladium, platinum,molybdenum, iron, ruthenium, osmium, rhodium, or iridium, individuallyor in combinations thereof. Useful catalyst may be heterogeneous orhomogeneous. In some embodiments, the catalysts are supported nickel orsponge nickel type catalysts.

In some embodiments, the hydrogenation catalyst comprises nickel thathas been chemically reduced with hydrogen to an active state (i.e.,reduced nickel) provided on a support. The support may comprise poroussilica (e.g., kieselguhr, infusorial, diatomaceous, or siliceous earth)or alumina. The catalysts are characterized by a high nickel surfacearea per gram of nickel.

Commercial examples of supported nickel hydrogenation catalysts includethose available under the trade designations “NYSOFACT”, “NYSOSEL”, and“NI 5248 D” (from BASF Catalysts LLC, Iselin, N.J.). Additionalsupported nickel hydrogenation catalysts include those commerciallyavailable under the trade designations “PRICAT 9910”, “PRICAT 9920”,“PRICAT 9908”, “PRICAT 9936” (from Johnson Matthey Catalysts, Ward Hill,Mass.).

The supported nickel catalysts may be of the type described in U.S. Pat.No. 3,351,566, U.S. Pat. No. 6,846,772, EP 0168091, and EP 0167201,incorporated by reference herein. Hydrogenation may be carried out in abatch or in a continuous process and may be partial hydrogenation orcomplete hydrogenation. In certain embodiments, the temperature rangesfrom about 50° C. to about 350° C., about 100° C. to about 300° C.,about 150° C. to about 250° C., or about 100° C. to about 150° C. Thedesired temperature may vary, for example, with hydrogen gas pressure.Typically, a higher gas pressure will require a lower temperature.Hydrogen gas is pumped into the reaction vessel to achieve a desiredpressure of H₂ gas. In certain embodiments, the H₂ gas pressure rangesfrom about 15 psig (1 atm) to about 3000 psig (204.1 atm), about 15 psig(1 atm) to about 90 psig (6.1 atm), or about 100 psig (6.8 atm) to about500 psig (34 atm). In certain embodiments, the reaction conditions are“mild,” wherein the temperature is approximately between approximately50° C. and approximately 100° C. and the H₂ gas pressure is less thanapproximately 100 psig. In other embodiments, the temperature is betweenabout 100° C. and about 150° C., and the pressure is between about 100psig (6.8 atm) and about 500 psig (34 atm). When the desired degree ofhydrogenation is reached, the reaction mass is cooled to the desiredfiltration temperature.

During hydrogenation, the carbon-carbon double bond containing compoundsin the olefins are partially to fully saturated by the hydrogen gas 48.In one embodiment, the resulting hydrogenated product 52 includeshydrocarbons with a distribution centered between approximately C₁₀ andC₁₂ hydrocarbons for naphtha- and kerosene-type jet fuel compositions.In another embodiment, the distribution is centered betweenapproximately C₁₆ and C₁₈ for a diesel fuel composition.

In certain embodiments, based upon the quality of the hydrogenatedproduct 52 produced in the hydrogenation unit 50, it may be preferableto isomerize the olefin hydrogenated product 52 to assist in targetingof desired fuel properties such as flash point, freeze point, energydensity, cetane number, or end point distillation temperature, amongother parameters. Isomerization reactions are well-known in the art, asdescribed in U.S. Pat. Nos. 3,150,205; 4,210,771; 5,095,169; and6,214,764, herein incorporated by reference. In one embodiment, theisomerization reaction at this stage may also crack some of the C₁₅₊compounds remaining, which may further assist in producing a fuelcomposition having compounds within the desired carbon number range,such as 5 to 16 for a jet fuel composition.

In certain embodiments, the isomerization may occur concurrently withthe hydrogenation step in the hydrogenation unit 50, thereby targeting adesired fuel product. In other embodiments, the isomerization step mayoccur before the hydrogenation step (i.e., the olefins 32 or center-cutolefins 42 may be isomerized before the hydrogenation unit 50). In yetother embodiments, it is possible that the isomerization step may beavoided or reduced in scope based upon the selection oflow-molecular-weight olefin(s) 14 used in the metathesis reaction.

In certain embodiments, the hydrogenated product 52 comprisesapproximately 15-25 weight % C₇, approximately <5 weight % C₈,approximately 20-40 weight % C₉, approximately 20-40 weight % C₁₀,approximately <5 weight % C₁₁, approximately 15-25 weight % C₁₂,approximately <5 weight % C₁₃, approximately <5 weight % C₁₄,approximately <5 weight % Cis, approximately <1 weight % C₁₆,approximately <1 weight % C₁₇, and approximately <1 weight % C₁₈+. Incertain embodiments, the hydrogenated product 52 comprises a heat ofcombustion of at least approximately 40, 41, 42, 43 or 44 MJ/kg (asmeasured by ASTM D3338). In certain embodiments, the hydrogenatedproduct 52 contains less than approximately 1 mg sulfur per kghydrogenated product (as measured by ASTM D5453). In other embodiments,the hydrogenated product 52 comprises a density of approximately0.70-0.75 (as measured by ASTM D4052). In other embodiments, thehydrogenated product has a final boiling point of approximately 220-240°C. (as measured by ASTM D86).

The hydrogenated product 52 produced from the hydrogenation unit 50 maybe used as a fuel composition, non-limiting examples of which includejet, kerosene, or diesel fuel. In certain embodiments, the hydrogenatedproduct 52 may contain byproducts from the hydrogenation, isomerization,and/or metathesis reactions. As shown in FIG. 1, the hydrogenatedproduct 52 may be further processed in a fuel composition separationunit 60, removing any remaining byproducts from the hydrogenated product52, such as hydrogen gas, water, C₂-C₉ hydrocarbons, or C₁₅+hydrocarbons, thereby producing a targeted fuel composition. In oneembodiment, the hydrogenated product 52 may be separated into thedesired fuel C₉-C₁₅ product 64, and a light-ends C₂-C₉ fraction 62and/or a C₁₅+ heavy-ends fraction 66. Distillation may be used toseparate the fractions. Alternatively, in other embodiments, such as fora naphtha- or kerosene-type jet fuel composition, the heavy endsfraction 66 can be separated from the desired fuel product 64 by coolingthe hydrogenated product 52 to approximately −40° C., −47° C., or −65°C. and then removing the solid, heavy ends fraction 66 by techniquesknown in the art such as filtration, decantation, or centrifugation.

With regard to the esters 34 from the distillation unit 30, in certainembodiments, the esters 34 may be entirely withdrawn as an ester productstream 36 and processed further or sold for its own value, as shown inFIG. 1. As a non-limiting example, the esters 34 may comprise varioustriglycerides that could be used as a lubricant. Based upon the qualityof separation between olefins and esters, the esters 34 may comprisesome heavier olefin components carried with the triglycerides. In otherembodiments, the esters 34 may be further processed in a biorefinery oranother chemical or fuel processing unit known in the art, therebyproducing various products such as biodiesel or specialty chemicals thathave higher value than that of the triglycerides, for example.Alternatively, in certain embodiments, the esters 34 may be partiallywithdrawn from the system and sold, with the remainder further processedin the biorefinery or another chemical or fuel processing unit known inthe art.

In certain embodiments, the ester stream 34 is sent to atransesterification unit 70. Within the transesterification unit 70, theesters 34 are reacted with at least one alcohol 38 in the presence of atransesterification catalyst. In certain embodiments, the alcoholcomprises methanol and/or ethanol. In one embodiment, thetransesterification reaction is conducted at approximately 60-70° C. andapproximately 1 atm. In certain embodiments, the transesterificationcatalyst is a homogeneous sodium methoxide catalyst. Varying amounts ofcatalyst may be used in the reaction, and, in certain embodiments, thetransesterification catalyst is present in the amount of approximately0.5-1.0 weight % of the esters 34.

The transesterification reaction may produce transesterified products 72including saturated and/or unsaturated fatty acid methyl esters(“FAME”), glycerin, methanol, and/or free fatty acids. In certainembodiments, the transesterified products 72, or a fraction thereof, maycomprise a source for biodiesel. In certain embodiments, thetransesterified products 72 comprise 9DA esters, 9UDA esters, and/or9DDA esters. Non-limiting examples of 9DA esters, 9UDA esters and 9DDAesters include methyl 9-decenoate (“9-DAME”), methyl 9-undecenoate(“9-UDAME”), and methyl 9-dodecenoate (“9-DDAME”), respectively. As anon-limiting example, in a transesterification reaction, a 9DA moiety ofa metathesized glyceride is removed from the glycerol backbone to form a9DA ester.

In another embodiment, a glycerin alcohol may be used in the reactionwith a glyceride stream. This reaction may produce monoglycerides and/ordiglycerides. In certain embodiments, the transesterified products 72from the transesterification unit 70 can be sent to a liquid-liquidseparation unit, wherein the transesterified products 72 (i.e., FAME,free fatty acids, and/or alcohols) are separated from glycerin.Additionally, in certain embodiments, the glycerin byproduct stream maybe further processed in a secondary separation unit, wherein theglycerin is removed and any remaining alcohols are recycled back to thetransesterification unit 70 for further processing.

In one embodiment, the transesterified products 72 are further processedin a water-washing unit. In this unit, the transesterified productsundergo a liquid-liquid extraction when washed with water. Excessalcohol, water, and glycerin are removed from the transesterifiedproducts 72. In another embodiment, the water-washing step is followedby a drying unit in which excess water is further removed from thedesired mixture of esters (i.e., specialty chemicals). Such specialtychemicals include non-limiting examples such as 9DA, 9UDA, and/or 9DDA,alkali metal salts and alkaline earth metal salts of the preceding,individually or in combinations thereof.

In one embodiment, the specialty chemical (e.g., 9DA) may be furtherprocessed in an oligomerization reaction to form a lactone, which mayserve as a precursor to a surfactant.

In certain embodiments, the transesterifed products 72 from thetransesterification unit 70 or specialty chemicals from thewater-washing unit or drying unit are sent to an ester distillationcolumn 80 for further separation of various individual or groups ofcompounds, as shown in FIG. 1. This separation may include, but is notlimited to, the separation of 9DA esters, 9UDA esters, and/or 9DDAesters. In one embodiment, the 9DA ester 82 may be distilled orindividually separated from the remaining mixture 84 of transesterifiedproducts or specialty chemicals. In certain process conditions, the 9DAester 82 should be the lightest component in the transesterified productor specialty chemical stream, and come out at the top of the esterdistillation column 80. In another embodiment, the remaining mixture 84,or heavier components, of the transesterified products or specialtychemicals may be separated off the bottom end of the column. In certainembodiments, this bottoms stream 84 may potentially be sold asbiodiesel.

The 9DA esters, 9UDA esters, and/or 9DDA esters may be further processedafter the distillation step in the ester distillation column. In oneembodiment, under known operating conditions, the 9DA ester, 9UDA ester,and/or 9DDA ester may then undergo a hydrolysis reaction with water toform 9DA, 9UDA, and/or 9DDA, alkali metal salts and alkaline earth metalsalts of the preceding, individually or in combinations thereof.

In certain embodiments, the fatty acid methyl esters from thetransesterified products 72 may be reacted with each other to form otherspecialty chemicals such as dimers.

Multiple, sequential metathesis reaction steps may be employed. Forexample, the metathesized natural oil product may be made by reacting anatural oil in the presence of a metathesis catalyst to form a firstmetathesized natural oil product. The first metathesized natural oilproduct may then be reacted in a self-metathesis reaction to formanother metathesized natural oil product. Alternatively, the firstmetathesized natural oil product may be reacted in a cross-metathesisreaction with a natural oil to form another metathesized natural oilproduct. Also in the alternative, the transesterified products, theolefins and/or esters may be further metathesized in the presence of ametathesis catalyst. Such multiple and/or sequential metathesisreactions can be performed as many times as needed, and at least one ormore times, depending on the processing/compositional requirements asunderstood by a person skilled in the art. As used herein, a“metathesized natural oil product” may include products that have beenonce metathesized and/or multiply metathesized. These procedures may beused to form metathesis dimers, metathesis trimers, metathesistetramers, metathesis pentamers, and higher order metathesis oligomers(e.g., metathesis hexamers, metathesis heptamers, metathesis octamers,metathesis nonamers, metathesis decamers, and higher than metathesisdecamers). These procedures can be repeated as many times as desired(for example, from 2 to about 50 times, or from 2 to about 30 times, orfrom 2 to about 10 times, or from 2 to about 5 times, or from 2 to about4 times, or 2 or 3 times) to provide the desired metathesis oligomer orpolymer which may comprise, for example, from 2 to about 100 bondedgroups, or from 2 to about 50, or from 2 to about 30, or from 2 to about10, or from 2 to about 8, or from 2 to about 6 bonded groups, or from 2to about 4 bonded groups, or from 2 to about 3 bonded groups. In certainembodiments, it may be desirable to use the metathesized naturalproducts produced by cross metathesis of a natural oil, or blend ofnatural oils, with a C₂-C₁₀ olefin, as the reactant in a self-metathesisreaction to produce another metathesized natural oil product.Alternatively, metathesized natural products produced by crossmetathesis of a natural oil, or blend of natural oils, with a C₂-C₁₀olefin can be combined with a natural oil, or blend of natural oils, andfurther metathesized to produce another metathesized natural oilproduct.

The metathesized natural oil product may have a number average molecularweight in the range from about 100 g/mol to about 150,000 g/mol, or fromabout 300 g/mol to about 100,000 g/mol, or from about 300 g/mol to about70,000 g/mol, or from about 300 g/mol to about 50,000 g/mol, or fromabout 500 g/mol to about 30,000 g/mol, or from about 700 g/mol to about10,000 g/mol, or from about 1,000 g/mol to about 5,000 g/mol. Themetathesized natural oil product may have a weight average molecularweight in the range from about from about 1,000 g/mol to about 100,000g/mol, from about 2,500 g/mol to about 50,000 g/mol, from about 4,000g/mol to about 30,000 g/mol, from about 5,000 g/mol to about 20,000g/mol, and from about 6,000 g/mol to about 15,000 g/mol. Themetathesized natural oil product may have a z-average molecular weightin the range from about from about 5,000 g/mol to about 1,000,000 g/mol,for example from about 7,500 g/mol to about 500,000 g/mol, from about10,000 g/mol to about 300,000 g/mol, or from about 12,500 g/mol to about200,000 g/mol. The polydispersity index is calculated by dividing theweight average molecular weight by the number average molecular weight.Polydispersity is a measure of the breadth of the molecular weightdistribution of the metathesized natural oil product, and such productsgenerally exhibit a polydispersity index of about 1 to about 20, or fromabout 2 to about 15. The number average molecular weight, weight averagemolecular weight, and z-average molecular weight may be determined bygel permeation chromatography (GPC), gas chromatography, gaschromatography mass-spectroscopy, NMR spectroscopy, vapor phaseosmometry (VPO), wet analytical techniques such as acid number, basenumber, saponification number or oxirane number, and the like. In someembodiments, gas chromatography and gas chromatography mass-spectroscopycan be used to analyze the metathesized natural oil product by firsttransforming the triglycerides to their corresponding methyl estersprior to testing. The extent to which the individual triglyceridemolecules have been polymerized can be understood as being directlyrelated to the concentration of diester molecules found in the analyzedfatty acid methyl esters. In some embodiments, the molecular weight ofthe metathesized natural oil product can be increased bytransesterifying the metathesized natural oil product with diesters. Insome embodiments, the molecular weight of the metathesized natural oilproduct can be increased by esterifying the metathesized natural oilproduct with diacids. In certain embodiments, the metathesized naturaloil product has a viscosity between about 1 centipoise (cP) and about10,000 centipoise (cP), between about 30 centipoise (cP) and about 5000cP, between about 50 cP and about 3000 cP, and from between about 80 cPand about 1500 cP.

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature, and pressure can be selected by oneskilled in the art to produce a desired product and to minimizeundesirable byproducts. The metathesis process may be conducted under aninert atmosphere. Similarly, if a reagent is supplied as a gas, an inertgaseous diluent can be used. The inert atmosphere or inert gaseousdiluent typically is an inert gas, meaning that the gas does notinteract with the metathesis catalyst to substantially impede catalysis.For example, particular inert gases are selected from the groupconsisting of helium, neon, argon, nitrogen, individually or incombinations thereof.

In certain embodiments, the metathesis catalyst is dissolved in asolvent prior to conducting the metathesis reaction. In certainembodiments, the solvent chosen may be selected to be substantiallyinert with respect to the metathesis catalyst. For example,substantially inert solvents include, without limitation, aromatichydrocarbons, such as benzene, toluene, xylenes, etc.; halogenatedaromatic hydrocarbons, such as chlorobenzene and dichlorobenzene;aliphatic solvents, including pentane, hexane, heptane, cyclohexane,etc.; and chlorinated alkanes, such as dichloromethane, chloroform,dichloroethane, etc. In one particular embodiment, the solvent comprisestoluene. The metathesis reaction temperature may be a rate-controllingvariable where the temperature is selected to provide a desired productat an acceptable rate. In certain embodiments, the metathesis reactiontemperature is greater than about −40° C., greater than about −20° C.,greater than about 0° C., or greater than about 10° C. In certainembodiments, the metathesis reaction temperature is less than about 150°C., or less than about 120° C. In one embodiment, the metathesisreaction temperature is between about 10° C. and about 120° C.

The metathesis reaction can be run under any desired pressure.Typically, it will be desirable to maintain a total pressure that ishigh enough to keep the cross-metathesis reagent in solution. Therefore,as the molecular weight of the cross-metathesis reagent increases, thelower pressure range typically decreases since the boiling point of thecross-metathesis reagent increases. The total pressure may be selectedto be greater than about 0.1 atm (10 kPa), in some embodiments greaterthan about 0.3 atm (30 kPa), or greater than about 1 atm (100 kPa).Typically, the reaction pressure is no more than about 70 atm (7000kPa), in some embodiments no more than about 30 atm (3000 kPa). Anon-limiting exemplary pressure range for the metathesis reaction isfrom about 1 atm (100 kPa) to about 30 atm (3000 kPa). In certainembodiments it may be desirable to run the metathesis reactions under anatmosphere of reduced pressure. Conditions of reduced pressure or vacuummay be used to remove olefins as they are generated in a metathesisreaction, thereby driving the metathesis equilibrium towards theformation of less volatile products. In the case of a self-metathesis ofa natural oil, reduced pressure can be used to remove C₁₂ or lighterolefins including, but not limited to, hexene, nonene, and dodecene, aswell as byproducts including, but not limited to cyclohexadiene andbenzene as the metathesis reaction proceeds. The removal of thesespecies can be used as a means to drive the reaction towards theformation of diester groups and cross linked triglycerides.

The metathesized natural oil compositions described herein may beutilized independently and/or incorporated into various formulations andused as functional ingredients in dimethicone replacements, laundrydetergents, fabric softeners, personal care applications, such asemollients, hair fixative polymers, rheology modifiers, specialtyconditioning polymers, surfactants, UV absorbers, solvents, humectants,occlusives, film formers, or as end use personal care applications, suchas cosmetics, lip balms, lipsticks, hair dressings, sun care products,moisturizer, fragrance sticks, perfume carriers, skin feel agents,shampoos/conditioners, bar soaps, hand soaps/washes, bubble baths, bodywashes, facial cleansers, shower gels, wipes, baby cleansing products,creams/lotions, and antiperspirants/deodorants.

The metathesized natural oil compositions described herein may also beincorporated into various formulations and used as functionalingredients in lubricants, functional fluids, fuels and fuel additives,additives for such lubricants, functional fluids and fuels,plasticizers, asphalt additives, friction reducing agents, antistaticagents in the textile and plastics industries, flotation agents, gellingagents, epoxy curing agents, corrosion inhibitors, pigment wettingagents, in cleaning compositions, plastics, coatings, adhesives, skinfeel agents, film formers, rheological modifiers, release agents,conditioners dispersants, hydrotropes, industrial and institutionalcleaning products, oil field applications, gypsum foamers, sealants,agricultural formulations, enhanced oil recovery compositions, solventproducts, gypsum products, gels, semi-solids, detergents, heavy dutyliquid detergents (HDL), light duty liquid detergents (LDL), liquiddetergent softeners, antistat formulations, dryer softeners, hardsurface cleaners (HSC) for household, autodishes, rinse aids, laundryadditives, carpet cleaners, softergents, single rinse fabric softeners,I&I laundry, oven cleaners, car washes, transportation cleaners, draincleaners, defoamers, anti-foamers, foam boosters, anti-dust/dustrepellants, industrial cleaners, institutional cleaners, janitorialcleaners, glass cleaners, graffiti removers, concrete cleaners,metal/machine parts cleaners, pesticides, agricultural formulations andfood service cleaners, plasticizers, asphalt additives and emulsifiers,friction reducing agents, film formers, rheological modifiers, biocides,biocide potentiators, release agents, household cleaning products,including liquid and powdered laundry detergents, liquid and sheetfabric softeners, hard and soft surface cleaners, sanitizers anddisinfectants, and industrial cleaning products, emulsionpolymerization, including processes for the manufacture of latex and foruse as surfactants as wetting agents, and in agriculture applications asformulation inerts in pesticide applications or as adjuvants used inconjunction with the delivery of pesticides including agricultural cropprotection turf and ornamental, home and garden, and professionalapplications, and institutional cleaning products, oil fieldapplications, including oil and gas transport, production, stimulationand drilling chemicals and reservoir conformance and enhancement,organoclays for drilling muds, specialty foamers for foam control ordispersancy in the manufacturing process of gypsum, cement wall board,concrete additives and firefighting foams, paints and coalescing agents,paint thickeners, or other applications requiring cold toleranceperformance or winterization (e.g., applications requiring cold weatherperformance without the inclusion of additional volatile components).

The following examples and data merely illustrate the invention. It isto be understood that various modifications thereof will become apparentto those skilled in the art upon reading the specification. Therefore,it is to be understood that the invention disclosed herein includes anysuch modifications that may fall within the scope of the appendedclaims.

EXAMPLES Multiple Metathesis Example

Physical Properties of Metathesized Soybean Oil (Samples A, B and C)

SAMPLE A Kinematic Kinematic Noack Viscosity @ Viscosity @ VolatilityPour Point 40° C. (ASTM 100° C. (ASTM Viscosity (ASTM (ASTM D97, D445,in cSt) D445, in cSt) Index D5800) in ° C.) 246 40 219 8.3 wt % 6

SAMPLE B Brookfield Viscosity Flash Point Pour Point (in cP) (ASTM D93,in ° C.) (ASTM D97, in ° C.) 295 177 3

SAMPLE C Once metathesized (1x) unstripped 135 cP Once metathesized (1x)stripped at 150° C. 262.5 cP Once metathesized (1x) stripped at 200° C.305 cP Twice metathesized (2x) unstripped 392.5 cP Twice metathesized(2x) stripped at 150° C. 567.5 cP Twice metathesized (2x) stripped at200° C. 650 cPViscosity measurements for Sample C were performed at 40° C.

Various Compositional Fractions of MSBO. Reference FIG. 2 and FIG. 3 forMass Spectra Analyses

Metathesis Reaction of Triolein (Oleyl Triglyceride) with Grubbs 2^(nd)Generation Catalyst

1 gram Triolein in a flask was heated to 45° C. under N₂ protection.0.01 gram Catalyst was added. They reaction was kept at 45° C. for 16hours and quenched with ethyl vinyl ether. The mixture was dissolved inEthyl acetate and filtered through celite. The MS of resultant sampleswas tested on a triple quadrupole mass spectrometer with electrosprayionization source for Micromass Quattro LC. Reference FIG. 4 and FIG. 5for mass spectra analyses.

Metathesis of Canola Oil to Generate FAME and Diesters

Refined bleached and deodorized canola oil (170 g) was loaded into a 250ml 2-neck round bottom flask with a magnetic stir bar. The top joint ofthe flask was fitted with a 320 mm cold coil condenser fed by a chillercirculator set to 15° C. To the top of the condenser was fitted a hoseadapter connected to an oil bubbler via Tygon tubing. The side arm neckwas fitted with a rubber septum through which was fed a needle typethermocouple and an 18 gauge stainless steel needle for the purpose ofsupplying the flask with a nitrogen source. The oil was heated, withmagnetic stirring, for 2 hr at 200° C. while being sparged with drynitrogen. After 2 hr, the oil was allowed to cool to 70° C., beforeadding the metathesis catalyst. The catalyst (Materia C827) was addedvia canola oil slurry through the top joint of the flask with a nitrogensweep being maintained throughout the slurry addition. At this time thecoil condenser was replaced. The reaction mixture was sparged withnitrogen an additional five minutes, to insure an inert atmosphere,before the nitrogen supply was closed. Metathesis was carried out for 3hr at 70° C., with no nitrogen sweep, before raising the temperature ofthe reaction mixture to 100° C. for the purpose of deactivating thecatalyst. Following 1 hr at 100° C., the reaction mixture was allowed tocool to ambient temperature overnight, under a slow nitrogen sweep.

The next day, the rubber septum was exchanged for PTFE thermocoupleadapter, and the coil condenser was exchanged for a short pathdistillation head with jacketed condenser equipped with a 100 mlreceiving flask. The reaction mixture was stripped to a pot temperatureof 250° C. at a pressure of 300 mTorr for 4.5 hr. Stripping resulted inthe removal of 17.4 wt. % lights and yielded a slightly burnt lookingoil product. Brookfield viscosity of the final product was measured as710 cP at 40° C. Conversion of the product to its corresponding fattyacid methyl esters was accomplished prior to analysis by gaschromatography. The resulting mixture of fatty acid methyl esters wasfound to contain 27 wt. % diesters as shown by gas chromatography.

Data Set #1 on Metathesized Natural Oil Compositions

In the Data Sets below, M_(n) refers to number average molecular weight,Mw refers to weight average molecular weight, M_(z) refers to z averagemolecular weight, PDI refers to polydispersity index, TGA refers tothermogravimetric analysis, and IV refers to intrinsic viscosity. Also,MSBO refers to metathesized soybean oil, MCO refers to metathesizedcanola oil, and 2× refers to twice metathesized.

Diester Viscosity Notebook # Product Description Content Mn Mw Mz PDI @40 C. TGA IV 1033-96-5 MSBO Stripped, 16.85 2461 6946 12987 2.82 281 cPn/a n/a filtered 1064-6-4 2XMSBO 2XMSBO 22.17 3034 12827 38689 4.23 650cP n/a 108.54  Stripped at 200° C. 1106-94-C MCBO Super gel 31.72 265327098 121316 10.21 Too Viscous n/a n/a to measure 1106-96-D MCO n/a n/a2982 11142 32490 3.74 700 cP n/a 77.52 1106-98-D MCO n/a n/a 2844 1060329450 3.73 750 cP n/a 91.17 1129-12-2 2XMSBO Stripped at 25.06 2336 969328181 4.15 642 cP 2.37% 85.62 200° C. 1129-13-1 MSBO Stripped at 24.262363 7363 18648 3.11 474 cP n/a n/a 200° C. 1129-13-2 2XMSBO Stripped atn/a n/a n/a n/a n/a n/a n/a n/a 200° C. BB9004 MSBO Stripped at 26.733393 20608 63294 6.07 1525 cP  n/a n/a 150° C. BB9012 MSBO Stripped at23.48 2933 15175 44975 5.17 990 cP n/a n/a 150° C. BB9013 MSBO Strippedat 23.29 3007 15899 47980 5.29 1215 cP  n/a n/a 150° C. BB9014 2XMSBO2XMSBO 23.17 2779 13302 45017 4.79 590 cP n/a 112.50  Stripped at 150°C. BB9015 2XMSBO 2XMSBO 23.03 2691 12142 41782 4.51 635 cP n/a 113.88 Stripped at 200° C.

Data Set #2 on Metathesized Natural Oil Compositions

Stripping Viscosity Sample no. Feedstock temp, ° C. 40° C. (CP) Mn Mw MzPDI Once metathesized (1X) BB9028 soy oil 200 305 NA NA NA NA Oncemetathesized (1X) BB9040 soy oil 200 285 2397  5913  13273  2.5 Twicemetathesized (2X) BB9035 BB9028 150 2930 2594 31089 110887 12.0 Twicemetathesized (2X) BB9039 BB9028 200 3244 2750 31235 105716 11.4 Twicemetathesized (2X) BB9047A BB9040 150 2660 NA NA NA NA Twice metathesized(2X) BB9047B BB9040 200 3050 2900 30819 102295 10.6 NOTE: All catalystloading = 38-42 ppm. All reaction temp = 70° C.

Data Set #3 on Metathesized Natural Oil Compositions

Stripping Viscosity Sample temp, 100° C. no. Feedstock ° C. (cSt) Oncemetathesized (1X) BB8089 Canola oil 200 88.4 Once metathesized (1X)BB8087 Canola oil 200 83.7 Once metathesized (1X) BB8092B Canola oil 20082.3 Twice metathesized (2X) BB8092D BB8092B 200 549.9

1-16. (canceled)
 17. A method of making a metathesized natural oilcomposition comprising one or more metathesis oligomers, the methodcomprising: providing natural oil glycerides, wherein the natural oilglycerides comprise metathesized natural oil glycerides, which areformed by the cross-metathesis of a natural oil glycerides with C₂-C₆low-molecular-weight olefins; and reacting the natural oil glycerides inthe presence of a metathesis catalyst to form metathesis oligomers;wherein the metathesis oligomers have a weight average molecular weightin the range from 1,000 g/mol to 100,000 g/mol.
 18. The method of claim17, wherein the metathesis oligomers have a weight average molecularweight in the range from 2,500 g/mol to 50,000 g/mol.
 19. The method ofclaim 18, wherein the metathesis oligomers have a weight averagemolecular weight in the range from 7,000 g/mol to 35,000 g/mol.
 20. Themethod of claim 1, wherein the C₂-C₆ low-molecular-weight olefins areselected from the group consisting of ethylene, propylene, 1-butene,2-butene, and isobutene.